Method of polymerization

ABSTRACT

This invention relates to a composition of matter represented by the formula below, and to a polymerization process comprising combining an olefin in the gas or slurry phase with an activator, a support and a compound represented by the following formula: 
                 
 
wherein
     M is a group 3 to 14 metal,   each X is independently an anionic leaving group,   n is the oxidation state of M,   m is the formal charge of the YZL ligand,   Y is a group 15 element,   Z is a group 15 element,   L is a group 15 or 16 element,   R 1  and R 2  are independently a C, to C 20  hydrocarbon group, a heteroatom containing group, silicon, germanium, tin, lead, phosphorus, a halogen,   R 1  and R 2  may also be interconnected to each other,   R 3  is absent, or is hydrogen, a group 14 atom containing group, a halogen, a heteroatom containing group,   R 4  and R 5  are independently an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, or multiple ring system,   R 6  and R 7  are independently absent or hydrogen, halogen, a heteroatom or a hydrocarbyl group, or a heteroatom containing group.

RELATED APPLICATION DATA

This application is a Divisional of U.S. patent application Ser. No.09/312,878 filed May 17, 1999, now issued as U.S. Pat. No. 6,271,325.

FIELD OF THE INVENTION

This invention relates to olefin polymerization catalysts containing ametal atom bound to at least two group 15 atoms and their use in gas orslurry phase to produce polyolefins.

BACKGROUND OF THE INVENTION

The intense commercialization of metallocene polyolefin catalysts(metallocene being cyclopentadienyl based transition metal catalystcompounds) has led to widespread interest in the design ofnon-metallocene, homogeneous catalysts, particularly for use in theeconomical gas and slurry phase processes. This field is more than anacademic curiosity as new, non-metallocene catalysts in gas or slurryphase may provide an easier, more economical pathway to currentlyavailable products and may also provide product and processopportunities which are beyond the capability of metallocene catalystsin the gas or slurry phase.

Anionic, multidentate heteroatom ligands have received the mostattention in non-metallocene polyolefins catalysis. Notable classes ofbidentate anionic ligands which form active polymerization catalystsinclude N—N and N ligand sets. Examples of these types ofnon-metallocene catalysts include amidopyridines (Kempe, R.,“Aminopyridinato Ligands —New Directions and Limitations”, 80^(th)Canadian Society for Chemistry Meeting, Windsor, Ontario, Canada, Jun.1-4, 1997. Kempe, R. et al, Inorg. Chem. 1996 vol 35 6742.) Likewise,recent reports by Jordan et al. of polyolefin catalysts based onhydroxyquinolines (Bei, X.; Swenson, D. C.; Jordan, R. F.,Organometallics 1997, 16, 3282) have been interesting even though thecatalytic activities of Jordan's hydroxyquinoline catalysts are low.

Schrock et al in U.S. Pat. No. 5,889,128 discloses a process for theliving polymerization of olefins in solution using initiators having ametal atom and a ligand having two group 15 atoms and a group 16 atom orthree group 15 atoms. In particular, the solution phase polymerizationof ethylene using {[NON]ZrMe} [MeB(C⁶F₅)₃1 or{[NON]ZrMe(PhNMe2)]}[B(C⁶F⁵)41 is disclosed in examples 9 and 10.

EP 893 454 A1 discloses unsupported transition metal amide compoundsused in combination with activators to polymerize olefins in thesolution phase.

Ethylenebis(salicylideneiminato)zirconium dichloride combined withmethyl alumoxane deposited on a support and unsupported versions wereused to polymerize ethylene by Repo et al in Macromolecules 1997, 30,171-175.

Thus there is a need in the art for gas or slurry phase processes toproduce polyolefins using new and different supported catalyst systems.

SUMMARY OF THE INVENTION

This invention relates to a catalytic molecule, and a catalyst systemcomprising a support, an activator, and a metal catalyst compound.

In one aspect, the invention relates to a catalyst system comprising asupport, an activator and a metal catalyst compound comprising a group 3to 14 metal atom bound to at least one anionic leaving group and alsobound to at least two group 15 atoms, at least one of which is alsobound to a group 15 or 16 atom through another group which may be a C₁to C₂₀ hydrocarbon group, a heteroatom containing group, silicon,germanium, tin, lead, phosphorus, or a halogen, wherein the group 15 or16 atom may also be bound to nothing or a hydrogen, a group 14 atomcontaining group, a halogen, or a heteroatom containing group, andwherein each of the two group 15 atoms are also bound to a cyclic groupand may optionally be bound to hydrogen, a halogen, a heteroatom or ahydrocarbyl group, or a heteroatom containing group.

This invention relates to the gas or slurry phase polymerization ofolefins using an olefin polymerization catalyst system comprising anactivator, a support and a transition metal compound represented by theformula:

wherein

-   M is a group 3 to 12 transition metal or a group 13 or 14 main group    metal,-   each X is independently an anionic leaving group,-   n is the oxidation state of M,-   m is the formal charge of the YZL ligand,-   Y is a group 15 element,-   Z is a group 15 element,-   L is a group 15 or 16 element,-   R¹ and R² are independently a C₁ to C₂₀ hydrocarbon group, a    heteroatom containing group, silicon, germanium, tin, lead,    phosphorus, halogen,-   R¹ and R² may also be interconnected to each other,-   R³ is absent, or is hydrogen, a group 14 atom containing group, a    halogen, a heteroatom containing group,-   R⁴ and R⁵ are independently an aryl group, a substituted aryl group,    a cyclic alkyl group, a substituted cyclic alkyl group, or multiple    ring system, and-   R⁶ and R⁷ are independently absent or hydrogen, halogen, heteroatom    or a hydrocarbyl group, or a heteroatom containing group.

By “formal charge of the YZL ligand” is meant the charge of the entireligand absent the metal and the leaving groups X.

By “R¹ and R² may also be interconnected to each other” is meant that R¹and R² may be directly bound to each other or may be bound to each otherthrough other groups.

The activator is preferably an aluminum alkyl, an alumoxane, a modifiedalumoxane, a non-coordinating anion, a borane, a borate or a combinationthereof.

In another aspect, the invention relates to a catalytic moleculecomprising the transition metal compound represented by the formula setforth above.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a catalytic molecule (metal catalyst),and a catalyst system comprising a support, an activator, and the metalcatalyst. The metal catalyst shows surprising ability to be immobilizedon a support, activated by an activator, and surprising robustness andcatalytic activity when supported and activated. The catalyst moleculeitself is described, hereinafter, with reference to its combination withan activator.

In a preferred embodiment the activator is combined with a compoundrepresented by the formula:

wherein

-   M is a group 3-12 transition metal or a group 13 or 14 main group    metal, preferably a-   group 4, 5, or 6 metal, preferably zirconium or hafniurn,-   each X is independently an anionic leaving group, preferably    hydrogen, a hydrocarbyl-   group, a heteroatom or a halogen,-   n is the oxidation state of M, preferably +3, +4, or +5, preferably    +4,-   m is the formal charge of the YZL ligand, preferably 0, -1, -2 or    -3, preferably −2,-   L is a group 15 or 16 element, preferably nitrogen,-   Y is a group 15 element, preferably nitrogen or phosphorus,-   Z is a group 15 element, preferably nitrogen or phosphorus,-   R¹ and R² are independently a C₁ to C₂₀ hydrocarbon group, a    heteroatom containing group having up to twenty carbon atoms,    silicon, germanium, tin, lead, phosphorus, a halogen, preferably a    C₂ to C₆ hydrocarbon group, preferably a C₂ to C₂₀ alkyl, aryl or    aralkyl group, preferably a linear, branched or cyclic C₂ to C₂₀    alkyl group, R¹ and R² may also be interconnected to each other,-   R³ is absent or a hydrocarbon group, hydrogen, a halogen, a    heteroatom containing group, preferably a linear, cyclic or branched    alkyl group having 1 to 20 carbon atoms, more preferably R³ is    absent or hydrogen,-   R⁴ and R⁵ are independently an aryl group, a substituted aryl group,    a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic    aralkyl group, a substituted cyclic aralkyl group or multiple ring    system, preferably having up to 20 carbon atoms, preferably between    3 and 10 carbon atoms, preferably a C, to C₂₋₀ hydrocarbon group, a    C] to C₂₋₀ aryl group or a C₁ to C₂₀ aralkyl group, and-   R⁶ and R⁷ are independently absent, or hydrogen, halogen, heteroatom    or a hydrocarbyl group, preferably a linear, cyclic or branched    alkyl group having 1 to 20 carbon atoms, more preferably absent.

An aralkyl group is defined to be a substituted aryl group.

In a preferred embodiment, L is bound to one of Y or Z and one of R¹ orR² is bound to L and not to Y or Z.

In an alternate embodiment R³ and L do not form a heterocyclic ring.

In a preferred embodiment R⁴ and R⁵ are independently a grouprepresented by the following formula:

wherein

-   R⁹ to R¹² are each independently hydrogen, a C₁ to C₄₀ alkyl group,    a heteroatom, a heteroatom containing group containing up to 40    carbon atoms, preferably a C, to C₂₀ linear or branched alkyl group,    preferably a methyl, ethyl, propyl or butyl group, any two R groups    may form a cyclic group and/or a heterocyclic group. The cyclic    groups may be aromatic. In a preferred embodiment R⁹, R¹⁰ and R¹²    are independently a methyl, ethyl, propyl or butyl group, in a    preferred embodiment R⁹, R¹⁰ and R¹² are methyl groups, and R⁸ and    R¹¹ are hydrogen.

In a particularly preferred embodiment R⁴ and R⁵ are both a grouprepresented by the following formula:

In this embodiment, M is preferably zirconium or hafnium, mostpreferably zirconium; each of L, Y, and Z is nitrogen; each of R¹ and R²is —CH₂—CH₂—; R³ is hydrogen; and R⁶ and R⁷ are absent.

These metal compounds are prepared by methods known in the art, such asthose disclosed in U.S. Pat. No. 5,889,128 and the references citedtherein which are all incorporated by reference herein. A preferreddirect synthesis of these compounds comprises reacting the neutralligand with M^(n)X_(n)(M is a group 3-14 metal, n is the oxidation stateof M, X is an anionic group, such as halide, in a non-coordinating orweakly coordinating solvent, such as ether, toluene, xylene, benzene,methylene chloride, and/or hexane or other solvent having a boilingpoint above 60° C., at about 20 to about 150° C. (preferably 20 to 100°C.), preferably for 24 hours or more, then treating the mixture with anexcess (such as four equivalents) of an alkylating agent, such as methylmagnesium bromide in ether. The magnesium salts are removed byfiltration, and the metal complex isolated by standard techniques.

In a preferred embodiment this invention relates to a method to preparea metal compound comprising reacting a neutral ligand with a compoundrepresented by the formula M^(nX) _(n) (where M is a group 3-14 metal, nis the oxidation state of M, X is an anionic leaving group) in anon-coordinating or weakly coordinating solvent, at about 20° C. orabove, preferably at about 20 to about 100° C., then treating themixture with an excess of an alkylating agent, then recovering the metalcomplex. In a preferred embodiment the solvent has a boiling point above60° C., such as ether, toluene, xylene, benzene, methylene chlorideand/or hexane.

This invention further relates to a method to prepare a metal adductcomprising reacting a neutral ligand with a compound represented by theformula M^(n)X_(n), (where M is Zr or Hf, n is the oxidation state of M,X is a halogen) in a non-coordinating or weakly coordinating solvent, at20° C. or more, preferably at about 20 to about 100° C. then recoveringthe metal adduct.

This invention further relates to the reaction product of a neutralligand reacted with a compound represented by the formula M^(n)X_(n)(where M is Zr or Hf, n is the oxidation state of M, X is an anionicleaving group), in a non-coordinating or weakly coordinating solvent atabout 20° C. or above, preferably at about 20 to about 100° C.

-   In a preferred embodiment the neutral ligand is represented by the    formula:-   Y is a group 15 element, preferably nitrogen or phorphorus,-   Z is a group 15 element, preferably nitrogen or phorphorus,-   L is a group 15 or 16 element, preferably nitrogen,-   R¹ and R² are independently a C₁ to C₂₀ hydrocarbon group, a    heteroatom containing group, silicon, germanium, tin, lead,    phosphorus, a halogen,-   R¹ and R² may also be interconnected to each other,-   R³ is absent, or is hydrogen, a group 14 atom containing group, a    halogen, a heteroatom containing group,-   R⁴ and R⁵ are independently an aryl group, a substituted aryl group,    a cyclic alkyl group, a substituted cyclic alkyl group, or multiple    ring system,-   R⁶ and R⁷ are independently absent or hydrogen, halogen, a    heteroatom or a hydrocarbyl group, or a heteroatom containing group.

The transition metal compounds described herein are preferably combinedwith one or more activators to form an olefin polymerization catalystsystem. Preferred activators include alkyl aluminum compounds (such asdiethylaluminum chloride), alumoxanes, modified alumoxanes,non-coordinating anions, non-coordinating group 13 metal or metalliodanions, boranes, borates and the like. It is within the scope of thisinvention to use alumoxane or modified alumoxane as an activator, and/orto also use ionizing activators, neutral or ionic, such as tri (n-butyl)ammonium tetrakis (pentafluorophenyl) boron or a trisperfluorophenylboron metalloid precursor which ionize the neutral metallocene compound.Other useful compounds include triphenyl boron, triethyl boron,tri-n-butyl ammonium tetraethylborate, triaryl borane and the like.Other useful compounds include aluminate salts as well.

There are a variety of methods for preparing alumoxane and modifiedalumoxanes, non-limiting examples of which are described in U.S. Pat.Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734,4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801,5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838,5,731,253 and 5,731,451 and European publications EP-A-0 561 476, EP-B10 279 586 and EP-A-0 594-218, and PCT publication WO 94/10180, all ofwhich are herein fully incorporated by reference.

Ionizing compounds may contain an active proton, or some other cationassociated with but not coordinated to or only loosely coordinated tothe remaining ion of the ionizing compound. Such compounds and the likeare described in European publications EP-A-0 570 982, EP-A-0 520 732,EP-A-0 495 375, EP-A-0 426 637, EP-A-500 944, EP-A-0 277 003 and EP-A-0277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197,5,241,025, 5,387,568, 5,384,299 and 5,502,124 and U.S. patentapplication Ser. No. 08/285,380, filed Aug. 3, 1994, all of which areherein fully incorporated by reference. Other activators include thosedescribed in PCT publication WO 98/07515 such as tris (2,2′,2″-nonafluorobiphenyl) fluoroaluminate, which is fully incorporatedherein by reference. Combinations of activators are also contemplated bythe invention, for example, alumoxanes and ionizing activators incombinations, see for example, PCT publications WO 94/07928 and WO95/14044 and U.S. Pat. Nos. 5,153,157 and 5,453,410 all of which areherein fully incorporated by reference. Also, methods of activation suchas using radiation and the like are also contemplated as activators forthe purposes of this invention.

In general the transition metal compound and the activator are combinedin ratios of about 1000:1 to about 0.5:1. In a preferred embodiment thetransition metal compound and the activator are combined in a ratio ofabout 300:1 to about 1:1, preferably about 10:1 to about 1:1, forboranes, borates, aluminates, etc. the ratio is preferably about 1:1 toabout 10:1 and for alkyl aluminum compounds (such as diethylaluminumchloride combined with water) the ratio is preferably about 0.5:1 toabout 10:1.

Polymerization Process of the Invention

The catalysts and catalyst systems described above are suitable for usein the polymerization process of the invention. The polymerizationprocess of the invention includes a solution, gas or slurry process or acombination thereof, most preferably a gas or slurry phase process.

In an embodiment, this invention is directed toward the slurry or gasphase polymerization or copolymerization reactions involving thepolymerization of one or more monomers having from 2 to 30 carbon atoms,preferably 2-12 carbon atoms, and ore preferably 2 to 8 carbon atoms.The invention is particularly well suited to the copolymerizationreactions involving the polymerization of one or more olefin monomers ofethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1, hexene-1,octene-1, decene-1,3-methyl-pentene-1, 3,5,5-trimethyl-hexene-1 andcyclic olefins or a combination thereof. Other monomers can includevinyl monomers, diolefins such as dienes, polyenes, norbornene,norbornadiene monomers. Preferably a copolymer of ethylene is produced,where the comonomer is at least one alphaolefin having from 4 to carbonatoms, preferably from 4 to 12 carbon atoms, more preferably from 4 to 8carbon atoms and most preferably from 4 to 7 carbon atoms. In analternate embodiment, the geminally disubstituted olefins disclosed inWO 98/37109 may be polymerized or copolymerized using the inventionherein described.

In another embodiment ethylene or propylene is polymerized with at leasttwo different comonomers to form a terpolymer. The preferred comonomersare a combination of alpha-olefin monomers having 4 to 10 carbon atoms,more preferably 4 to 8 carbon atoms, optionally with at least one dienemonomer. The preferred terpolymers include the combinations such asethylenetbutene-1/hexene-1, ethylenelpropylene/butene-1,propylene/ethylene/hexene-1, ethylene/propylene/norbornene and the like.

In a particularly preferred embodiment the process of the inventionrelates to the polymerization of ethylene and at least one comonomerhaving from 4 to 8 carbon atoms, preferably 4 to 7 carbon atoms.Particularly, the comonomers are butene-1,4-methyl-pentene-1, hexene-1and octene-1, the most preferred being hexene-1 and/or butene-1.

Typically in a gas phase polymerization process a continuous cycle isemployed where in one part of the cycle of a reactor system, a cyclinggas stream, otherwise known as a recycle stream or fluidizing medium, isheated in the reactor by the heat of polymerization. This heat isremoved from the recycle composition in another part of the cycle by acooling system external to the reactor. Generally, in a gas fluidizedbed process for producing polymers, a gaseous stream containing one ormore monomers is continuously cycled through a fluidized bed in thepresence of a catalyst under reactive conditions. The gaseous stream iswithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product is withdrawn from the reactor and freshmonomer is added to replace the polymerized monomer. (See for exampleU.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749,5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661 and 5,668,228 allof which are fully incorporated herein by reference.)

The reactor pressure in a gas phase process may vary from about 10 psig(69 kPa) to about 500 psig (3448 kPa), preferably in the range of fromabout 100 psig (690 kPa) to about 400 psig (2759 kPa), preferably in therange of from about 200 psig (1379 kPa) to about 400 psig (2759 kPa),more preferably in the range of from about 250 psig (1724 kPa) to about350 psig (2414 kPa).

The reactor temperature in the gas phase process may vary from about 30°C. to about 120° C., preferably from about 60° C. to about 115° C., morepreferably in the range of from about 70° C. to 110° C., and mostpreferably in the range of from about 70° C. to about 95° C.

The productivity of the catalyst or catalyst system is influenced by themain monomer partial pressure. The preferred mole percent of the mainmonomer, ethylene or propylene, preferably ethylene, is from about 25 to90 mole percent and the monomer partial pressure is in the range of fromabout 75 psia (517 kPa) to about 300 psia (2069 kPa), which are typicalconditions in a gas phase polymerization process.

In a preferred embodiment, the reactor utilized in the present inventionand the process of the invention produce greater than 500 lbs of polymerper hour (227 Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or higher ofpolymer, preferably greater than 1000 lbs/hr (455 Kg/hr), morepreferably greater than 10,000 lbs/hr (4540 Kg/hr), even more preferablygreater than 25,000 lbs/hr (11,300 Kg/hr), still more preferably greaterthan 35,000 lbs/hr (15,900 Kg/hr), still even more preferably greaterthan 50,000 lbs/hr (22,700 Kg/hr) and most preferably greater than65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr (45,500Kg/hr).

Other gas phase processes contemplated by the process of the inventioninclude those described in U.S. Pat. Nos. 5,627,242, 5,665,818 and5,677,375, and European publications EP-A-0 794 200, EP-A-0 802 202 andEP-B-634 421 all of which are herein fully incorporated by reference.

A slurry polymerization process generally uses pressures in the range offrom about 1 to about 50 atmospheres and even greater and temperaturesin the range of 0° C. to about 120° C. In a slurry polymerization, asuspension of solid, particulate polymer is formed in a liquidpolymerization diluent medium to which ethylene and comonomers and oftenhydrogen along with catalyst are added. The suspension including diluentis intermittently or continuously removed from the reactor where thevolatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization mediurn is typically an alkane havingfrom 3 to 7 carbon atoms, preferably a branched alkane. The mediumemployed should be liquid under the conditions of polymerization andrelatively inert. When a propane medium is used the process must beoperated above the reaction diluent critical temperature and pressure.Preferably, a hexane or an isobutane medium is employed.

In one embodiment, a preferred polymerization technique of the inventionis referred to as a particle form polymerization, or a slurry processwhere the temperature is kept below the temperature at which the polymergoes into solution. Such technique is well known in the art, anddescribed in for instance U.S. Pat. No. 3,248,179 which is fullyincorporated herein by reference. The preferred temperature in theparticle form process is within the range of about 185° F. (85° C.) toabout 230° F. (I 10° C.). Two preferred polymerization methods for theslurry process are those employing a loop reactor and those utilizing aplurality of stirred reactors in series, parallel, or combinationsthereof. Non-limiting examples of slurry processes include continuousloop or stirred tank processes. Also, other examples of slurry processesare described in 4 U.S. Pat. No. 4,613,484, which is herein fullyincorporated by reference.

In another embodiment, the slurry process is carried out continuously ina loop reactor. The catalyst as a slurry in isobutane or as a dry freeflowing powder is injected regularly to the reactor loop, which isitself filled with circulating slurry of growing polymer particles in adiluent of isobutane containing monomer and comonomer. Hydrogen,optionally, may be added as a molecular weight control. The reactor ismaintained at pressure of about 525 psig to 625 psig (3620 kPa to 4309kPa) and at a temperature in the range of about 140° F. to about 220° F.(about 60° C. to about 104° C.) depending on the desired polymerdensity. Reaction heat is removed through the loop wall since much ofthe reactor is in the form of a double-jacketed pipe. The slurry isallowed to exit the reactor at regular intervals or continuously to aheated low pressure flash vessel, rotary dryer and a nitrogen purgecolumn in sequence for removal of the isobutane diluent and allunreacted monomer and comonomers. The resulting hydrocarbon free powderis then compounded for use in various applications.

In an embodiment the reactor used in the slurry process of the inventionis capable of and the process of the invention is producing greater than2000 lbs of polymer per hour (907 Kg/hr), more preferably greater than5000 lbs/hr (2268 Kg/hr), and most preferably greater than 10,000 lbs/hr(4540 Kg/hr). In another embodiment the slurry reactor used in theprocess of the invention is producing greater than 15,000 lbs of polymerper hour (6804 Kg/hr), preferably greater than 25,000 lbs/hr (11,340Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

In another embodiment in the slurry process of the invention the totalreactor pressure is in the range of from 400 psig (2758 kPa) to 800 psig(5516 kPa), preferably 450 psig (3103 kPa) to about 700 psig (4827 kPa),more preferably 500 psig (3448 kPa) to about 650 psig (4482 kPa), mostpreferably from about 525 psig (3620 kPa) to 625 tI psig (4309 kPa).

In yet another embodiment in the slurry process of the invention theconcentration of ethylene in the reactor liquid medium is in the rangeof from about 1 to 10 weight percent, preferably from about 2 to about 7weight percent, more preferably from about rOJ 2.5 to about 6 weightpercent, most preferably from about 3 to about 6 weight percent. Apreferred process of the invention is where the process, preferably aslurry or gas phase process is operated in the absence of or essentiallyfree of any scavengers, such as triethylaluminum, trimethylaluminum,tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminumchloride, dibutyl zinc and the like. This preferred process is describedin PCT publication WO 96/08520 and U.S. Pat. No. 5,712,352, which areherein fully incorporated by reference.

In another preferred embodiment the one or all of the catalysts arecombined with up to 10 weight % of a metal stearate, (preferably aaluminum stearate, more preferably aluminum distearate) based upon theweight of the catalyst, any support and the stearate, preferably 2 to 3weight %. In an alternate embodiment a solution of the metal stearate isfed into the reactor. In another embodiment the metal stearate is mixedwith the catalyst and fed into the reactor separately. These agents maybe mixed with the catalyst or may be fed into the reactor in a solutionwith or without the catalyst system or its components.

The catalyst and/or the activator may be placed on, deposited on,contacted with, incorporated within, adsorbded, or absorbed in asupport. Typically the support can be of any of the solid, poroussupports, including microporous supports. Typical support materialsinclude talc; inorganic oxides such as silica, magnesium chloride,alumina, silica-alumina; polymeric supports such as polyethylene,polypropylene, polystyrene, cross-linked polystyrene; and the like.Preferably the support is used in finely divided form. Prior to use thesupport is preferably partially or completely dehydrated. Thedehydration may be done physically by calcining or by chemicallyconverting all or part 43 of the active hydroxyls. For more informationon how to support catalysts please see U.S. Pat. No. 4,808,561 whichdiscloses how to support a metallocene catalyst system. The techniquesused therein are generally applicable for this invention.

In a preferred embodiment, the polyolefin recovered typically has a meltindex as measured by ASTM D-1238, Condition E, at 190° C. of 3000 g/10min or less. In a preferred embodiment the polyolefin is ethylenehomopolymer or copolymer. In a preferred embodiment for certainapplications, such as films, molded article and the like a melt index of100 g/10 min or less is preferred. For some films and molded article amelt index of 10 g/10 min is preferred. In a preferred embodiment thepolymer produced has a molecular weight of 200,000 Daltons or more.

In a preferred embodiment the catalyst system described above is used tomake a polyethylene having a density of between 0.88 and 0.970 g/cm³ (asmeasured by ASTM 2839), a melt index of 1.0 or less g/10 min or less (asmeasured by ASTM D-1238, Condition E, at 190° C.). Polyethylene having amelt index of between 0.01 to 10 dg/min is preferably produced. In someembodiments, a density of 0.915 to 0.940 g/cm³ would be preferred, inother embodiments densities of 0.930 to 0.960 g/cm³ are preferred.

The polyolefins then can be made into films, molded articles, sheets,wire and cable coating and the like. The films may be formed by any ofthe conventional technique known in the art including extrusion,co-extrusion, lamination, blowing and casting. The film may be obtainedby the flat film or tubular process which may be followed by orientationin an uniaxial direction or in two mutually perpendicular directions inthe plane of the film to the same or different extents. Orientation maybe to the same extent in both directions or may be to different extents.Particularly preferred methods to form the polymers into films includeextrusion or coextrusion on a blown or cast film line.

The films produced may further contain additives such as slip,antiblock, antioxidants, pigments, fillers, antifog, UV stabilizers,antistats, polymer processing aids, neutralizers, lubricants,surfactants, pigments, dyes and nucleating agents. Preferred additivesinclude silicon dioxide, synthetic silica, titanium dioxide,polydimethylsiloxane, calcium carbonate, metal stearates, calciumstearate, zinc stearate, talc, BaSO₄, diatomaceous earth, wax, carbonblack, flame retarding additives, low molecular weight resins,hydrocarbon resins, glass beads and the like. The additives may bepresent in the typically effective amounts well known in the art, suchas 0.001 weight % to 10 weight %.

This invention further relates to a library of a plurality of metalcompounds represented by the formula above. These libraries may then beused for the simultaneous parallel screening of catalysts by combiningthe library with one or more olefins, preferably in order to determinethe relative capabilities of the different compounds.

EXAMPLES

Mn and Mw were measured by gel permeation chromatography on a waters150° C. GPC instrument equipped with differential refraction indexdetectors. The GPC columns were calibrated by running a series of narrowpolystyrene standards and the molecular weights were calculated usingMark Houwink coefficients for the polymer is question.

Density was measured according to ASTM D 1505.

Melt Index (MI) 12 and 121 were measured according to ASTM D-1238,Condition E, at 190° C.

Melt Index Ratio (MIR) is the ratio of 121 over 12 as determined by ASTMD-1238.

Weight % comonomer was measured by proton NMR.

MWD=Mw/Mn

Example 1 Catalyst A Preparation

Preparation of [iPrNH(o-C₆₁₄)]₂O

A 250 mL one-neck flask was charged with [H₂N(o-C₆H₄)]₂O (10.0 g, 50Mmol), acetone (15 mL), activated Zn duist (25.0 g, 382 mmol) andglacial acetic acid (100 mL). The flask was capped with a rubber septum,connected to an oil-bubbler via a needle and then heated under rapidstirring to 60° C. for 24 h. After cooling to room temperature thereaction mixture was poured onto ice (200 mL), concentrated aqueous NH3(200 mL), and methylene chloride (150 mL). The layers were separated andthe aqueous layer extracted with methylene chloride (2×100 mL). Thecombined methylene chloride layers were dried over MgSO₄. Removal ofmethylene chloride in vacuo afforded crude material as an orange oil.The oil was dissolved in acetone (150 mL) and concentrated HCl (10 mL)was added. Within one minute colorless crystals began to form. Themixture was allowed to stand overnight and the colorless crystallinesolid was isolated by filtration, washed with acetone, and driedovernight under vacuum. A mixture of aqueous NaOH (100 mL, 10%) andether (100 mL) was added to this solid. The mixture was stirred untilthe solid dissolved. The layers were separated and the aqueous layerextracted with ether (3×50 mL). The combined organic layers were driedover MgSO₄. Activated charcoal was added prior to filtering through abed of Celite. Ether was removed in vacuo leaving a pale yellow oil(yield: 13.2 g, 93%). ¹H NMR (C₆D₆) δ6.98(t, 2), 6.63 (d, 2), 6.55 (t,2), 4.14 (br s, 2), 3.37 (br m, 2), 0.89 (d, 12). ¹³C NMR (C₆D₆)δ 144.8,140.0, 125.1, 118.8, 117.1, 112.5, 44.4, 23.2.

Preparation of {[iPrN(o-C₆H₄|₂O}ZrCl₂·C₇H₈

{iPrNH(o-C₆H₄)]₂O (3.02 g, 10.6 mmol) and Zr(NMe₂)₄ (2.84 g, 10.6 mmol)were dissolved in pentane (40 mL). The solution was stirred at roomtemperature for 3 h. All volatile components were removed in vacuo togive an oil. To this oil was added toluene (40 mL) and Me₃SiCI (2.9 g,26.7 mmol). The solution quickly turned bright orange and was left tostand at room temperature for 14 h. Small amounts of solid were removedby filtration and pentane (40 mL) added. The solution was cooled to −25°C. for 24 h. A solid was isolated by filtration (4.11 g, 72%). Accordingto ¹H NMR spectroscopy one equivalent of toluene was present. ¹H NMR(CD₂Cl₂, resonances for toluene are not given) δ 7.67 (d, 2), 7.08 (t,2), 6.83 (d, 2), 6.77 (t, 2), 4.66 (sept, 2), 1.52 (d, 12). ¹³C (3 NMR(CD₂CI₂, toluene resonances not given) δ 148.2, 143.4, 126.1, 117.7,114.7, 113.8, to 48.9, 20.0. Analysis calculated for C₂₅H₃₀Cl₂N₂OZr: C,55.95; H, 5.63, N, 5.22. Found: C, 55.84; H, 5.61; N, 5.27.

To 1.239 g of MAO (4.131 g of a 30 weight percent solution in toluene,j5 Albemarle) and 4.274 g of toluene in a 250 mL round bottom flask wasadded 0.037 g of {[iPrN(o-C₆H₃)]₂O}ZrCl₂·C₇H₈. The solution was stirredfor 15 minutes. 3.098 g of RU silica (Davison 948, calcined at 800° C.)was added followed by mixing. The mixture was dried overnight undervacuum yielding 4.114 g of finished catalyst with a loading of 0.14weight percent zirconium and an Al/Zr ratio of 310:1.

Example 2 Slurry-Phase Ethylene-Hexene Polymerization

Polymerization was performed in the slurry-phase in a 1-liter autoclavereactor equipped with a mechanical stirrer, an external water jacket fortemperature control, a septum inlet and vent line, and a regulatedsupply of dry nitrogen and ethylene. The reactor was dried and degassedat 160° C. Isobutane (400 mL) was added as a diluent, 35 mL of 1-hexene,and 0.4 mL of a 25 weight percent triisobutyl aluminum solution inhexane was added as a scavenger using a gas tight syringe. The reactorwas heated to 60° C. 0.256 g of finished catalyst A was added withethylene pressure and the reactor was pressurized with 79 psi (545 kpa)of ethylene. The polymerization was continued for 30 minutes whilemaintaining the reactor at 60° C. and 79 psi (545 kPa) by constantethylene flow. The reaction was stopped by rapid cooling and venting. Nopolymer was recovered.

Example 3 Catalyst B Preparation

To 1.902 g of MAO (6.340 g of a 30 weight percent solution in toluene,Albemarle) and 6.521 g of toluene in a 250 mL round bottom flask wasadded 0.126 g of {[(CD3)₂MeCN(o-C₆H₃)]20}ZrCl2. The solution was stirredfor 15 minutes. 5.003 g of silica (Davison 948, calcined at 600° C.) wasadded followed by mixing. The mixture was dried overnight under vacuumyielding 6.869 g of finished catalyst with a loading of 0.35 weightpercent zirconium and an Al/Zr ratio of 123:1. The{[(CD3)₂MeCN(o-C₆H₃)]20}ZrCl₂ was prepared according to the method inBaumann, Journal of the American Chemical Society, Vol 119, pg 3830,1997.

Example 4 Slurry-Phase Ethylene-Hexene Polymerization

Polymerization was performed in the slurry-phase in a 2-liter autoclavereactor equipped with a mechanical stirrer, an external water jacket fortemperature control, a septum inlet and vent line, and a regulatedsupply of dry nitrogen and ethylene. The reactor is dried and degassedat 100° C. Hexane (800 mL) is added as a diluent, 90 mL of 1-hexene, and0.2 mL of a 25 weight percent triethyl aluminum solution in heptane isadded as a scavenger using a gas tight syringe. The reactor was heatedto 60° C. 0.400 g of finished catalyst B was added with nitrogenpressure and the reactor was pressurized with 75 psi (545 kPa) ofethylene. The polymerization was continued for 30 minutes whilemaintaining the reactor at 60° C. and 75 psi (517 kPa) by constantethylene flow. The reaction was stopped by rapid cooling and venting.8.8 g of ethylene-hexene copolymer were recovered (MW=281, 700,MWD=4.68, 5.6 weight percent hexene, activity=229 g PE/mmol cat·atm·h).

Example 5 Catalyst C Preparation

To 2.034 g of MAO (6.783 g of a 30 weight percent solution in toluene,Albemarle) and 7.216 g of toluene in a 250 mL round bottom flask wasadded 0.130 g of {[(2,6-Me2C₆H₃)NCH2CH2]2O}ZrCI2. The solution wasstirred for 15 minutes. 5.024 g of silica (Davison 948, calcined at 800°C.) was added followed by mixing. The mixture was dried overnight undervacuum yielding 7.131 g of finished catalyst with a loading of 0.35weight percent zirconium and an Al/Zr ratio of 127:1. The([(2,6Me₂C₆H₃)NCH₂CH_(2]20)}ZrCI₂ was synthesized according to themethod of Aizenberg, Organometallics, vol. 17, pg 4795, 1998.

Example 6 Slurry-Phase Ethylene-Hexene Polymerization

The polymerization was conducted as per example 4. 0.200 g of finishedcatalyst C yielded 37.4 g of ethylene-hexene copolymer (MW=259,900,MWD=6.63, 5.6 weight percent hexene, activity=1950 g PE/nmuolcat·atm·h).

Example 7 Catalyst D Preparation

Preparation of [(2,4,6Me₃C₆H₂)NHCH₂CH_(2]) ₂NH

A 2 L one-armed Schlenk flask was charged with a magnetic stir bar,diethylenetriamine (23.450 g, 0.227 mol), mesityl bromide (90.51 g,0.455 mol), tris(dibenzylideneacetone) dipalladium (1.041 g, 1.14 mmol),racemic-2,2-bis(diphenylphosphino)-1,1′-binaphthyl (2.123 g, 3.41 mmol),sodium tert-butoxide (65.535 g, 0.682 mol), and toluene (800 mL). Thereaction mixture was heated to 95° C. and stirred. After 4 days thereaction was complete, as judged by proton NMR spectroscopy. All solventwas removed under vacuum and the residues dissolved in diethyl ether (1L). The ether was washed three times with water (1 L) and saturatedaqueous NaCl (500 mL) and dried over magnesium sulfate. Removal of theether in vacuo yielded a red oil which was dried at 70° C. for 12 hunder vacuum (yield: 71.10 g, 92%). ¹H NMR δ6.83 (s, 4), 3.39 (br s, 2),2.86 (t, 4), 2.49 (t, 4), 2.27 (s, 12), 2.21 (s, 6), 0.68 (br s, 1). ¹³CNMR δ143.74, 131.35, 129.83, 129.55, 50.17, 48.56, 20.70, 18.51.

Preparation of {([(2,4,6-Me3C₆H₂)NCH₂CH_(2]) ₂NH}ZrMe₂

10.798 g of [(2,4,6-Me₃C₆H₂)NHCH₂CH_(2]2)NH (31.8 mmol) was dissolved in250 mL of toluene in a 500 mL round bottom flask. 7.411 g of ZrC4 (31.8mmol) was added as a solid and the mixture heated to 80° C. withstirring for 24 hours. The mixture was cooled to room temperature (theinsoluble product {[(2,4,6Me₃C₆H₂)NHCH₂CH₂]2NH}ZrC₁₄ can be isolated byfiltration and stored for future use) and 43.5 mL of MeMgBr (3.0 M inether, 130.3 mmol) added dropwise with stirring over 30 minutes. Themixture was stirred for 60 minutes followed by filtration to removeMgClBr. The toluene and ether were removed under vacuum and the solidsextracted with toluene (200 mL). The volume of toluene was reduced to 10mL and 250 mL of pentane added causing the precipitation of a pale brownsolid. The solid product was isolated by filtration, washed with 50 mLof cold pentane, and dried under vacuum (15.201 g, 86% yield). ¹H NMR(C⁶D6, δ) 6.98 (s, 2), 6.96 (s, 2), 3.32 (m, 2), 3.12 (m, 2), 2.54 (s,6), 2.42 (s, 6), 2.36 (m, 4), 2.21 (s, 6), 1.16 (s, 1), 0.24 (s, 3),0.07 (s, 3). ¹³C NMR (C⁶D₆, δ) 146.56, 136.07, 135.55, 134.23, 130.29,129.98, 57.46, 51.27, 42.45, 39.63, 21.44, 19.39, 19.28. Analysiscalculated for C₂₄H₃₇N₃Zr: C, 62.83; H, 8.13; N, 9.16. Found: C, 62.91;H, 8.02; N, 9.04.

To 0.617 g of MAO (2.058 g of a 30 weight percent solution in toluene,Albemarle) and 3.009 g of toluene in a 250 mL round bottom flask wasadded 0.080 g of {[(2,4,6-Me3C₆H₂)NCH2CH2]2NH}ZrMe2. The solution wasstirred for 15 minutes. 3.000 g of silica (Davison 948, calcined at 800°C.) was added followed by mixing. The mixture was dried overnight undervacuum yielding 3.528 g of finished catalyst with a loading of 0.43weight percent zirconium and an Al/Zr ratio of 61:1.

Example 8 Slurry-Phase Ethylene-Hexene Polymerization

Polymerization was performed in the slurry-phase in a 1-liter autoclavereactor equipped with a mechanical stirrer, an external water jacket fortemperature control, a septum inlet and vent line, and a regulatedsupply of dry nitrogen and ethylene. The reactor was dried and degassedat 160° C. Isobutane (400 mL) was added as a diluent, 35 mL of 1-hexene,and 0.7 mL of a 25 weight percent trioctyl aluminum solution in hexanewas added as a scavenger using a gas tight syringe. The reactor washeated to 60° C. 0.078 g of finished catalyst D was added with ethylenepressure and the reactor was pressurized with 74 psi (510 kPa) ofethylene. The polymerization was continued for 30 minutes whilemaintaining the reactor at 60° C. and 74 psi (510 kPa) by constantethylene flow. The reaction was stopped by rapid cooling and venting.59.2 g of ethylene-hexene copolymer were recovered (MW=578,900,MWD=5.40, 11.8 weight percent hexene, activity=6530 g PE/mmolcat·atm·h).

Example 9 Catalyst E Preparation

To 11.230 g of MAO (37.434 g of a 30 weight percent solution in toluene,Albemarle) and 43.002 g of toluene in a 500 mL round bottom flask wasadded 0.742 g of {[(2,4,6 Me₃C₆H₂)NCH₂CH₂]2 NH}ZrMe₂. (Synthesizedaccording to the procedure in Example 7.) The solution was stirred for15 minutes. 30.002 g of silica (Davison 948, calcined at 600° C.) wasadded followed by mixing. The mixture was dried overnight under vacuumyielding 41.002 g of finished catalyst with a loading of 0.35 weightpercent zirconium and an Al/Zr ratio of 120:1.

Example 10 Gas-Phase Ethylene-Hexene Polymerization

Catalyst E described above was used for ethylene-hexene copolymerizationstudies described below. A continuous fluid bed gas-phase reactoroperated at 300 psi (2.07 MPa) total pressure and 1.64 fts (0.5m/s)cycle gas velocity was used for determining catalyst efficiency,ability to incorporate comonomer (1-hexene) and molecular weightcapability. The polymer properties were as follows: 8.4 weight percenthexene, MI₂=0.31, MI₂₁=13.53, MIR=43.65, density 0.9243 glcm³. A summaryof the process data is included in Table 1.

TABLE 1 H₂ conc. (ppm) 6451 C₂ conc. (mol %) 35.0 Hexene conc. (mol %)0.40 H₂/C₂ Ratio 184.5 C₆/C₂ Ratio 0.087 Reactor Temp (F/C) 145/62.8Avg. Bed weight (g) 1891 Production (g/h) 315 Residence Time (h) 6.0Productivity (g/g) − MB¹ 696 Productivity (g/g) − XRF² 1171 Total BedTurnovers 3.0 ¹MB = Material Balance ²XRF = X-ray Fluoresence

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures. As isapparent form the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly it is not intended thatthe invention be limited thereby.

1. A method to prepare a metal compound comprising reacting a neutralligand with a compound represented by the formula M^(n)X^(n) where M isa group 3-14 metal, n is the oxidation state of M, and X is an anionicgroup in a non-coordinating or weakly coordinating solvent, at about 20to about 100° C., then treating the mixture with an excess of analkylating agent, then recovering the metal complex and wherein theneutral ligand is represented by the formula:

where Y is a group 15 element, Z is a group 15 element, L is a group 15or 16 element, R¹ and R² are independently a C₁ to C₀ hydrocarbon group,a heteroatom containing group, silicon, germanium, tin, lead, orphosphorus, R¹ and R² may be interconnected to each other, R³ is absent,hydrogen, a group 14 atom containing group, a halogen, or a heteroatomcontaining group, R⁴ and R⁵ are independently an aryl group, asubstituted aryl group, a cyclic alkyl group, a substituted cyclic alkylgroup, or a multiple ring system, R⁶ and R⁷ are independently absent,hydrogen, halogen, a heteroatom, a hydrocarbyl group, or a heteroatomcontaining group.
 2. The method of claim 1 wherein the solvent has aboiling point above 60° C.
 3. The method of claim 1 wherein the solventis ether, toluene, xylene, benzene, methylene chloride and/or hexane. 4.A method to prepare a metal adduct comprising reacting a neutral ligandwith a compound represented by the formula M^(n)X_(n) where M is Zr orHf, n is the oxidation state of M, X is a halogen in a non-coordinatingor weakly coordinating solvent, at 20° C. or more, then recovering themetal adduct; and wherein the neutral ligand is represented by theformula:

where Y is a group 15 element, Z is a group 15 element, L is a group 15or 16 element, R¹ and R² are independently a C₁ to C₂₀ hydrocarbongroup, a heteroatom containing group, silicon, germanium, tin, lead, orphosphorus, R¹ and R² may be interconnected to each other, R³ is absent,hydrogen, a group 14 atom containing group, a halogen, or a heteroatomcontaining group, R⁴ and R⁵ are independently an aryl group, asubstituted aryl group, a cyclic alkyl group, a substituted cyclic alkylgroup, or a multiple ring system, R⁶ and R⁷ are independently absent,hydrogen, halogen, a heteroatom, a hydrocarbyl group, or a heteroatomcontaining group.